Alpha olefin oligomerization catalyst

ABSTRACT

A process for the preparation of linear olefins which comprises polymerizing ethylene in a hydrocarbon solvent at a temperature of 50°-150° C. in the presence of a catalyst comprising a zirconium metal compound, an organometallic compound wherein the metal is selected from the group consisting of zinc, magnesium and aluminum, and a basic salt of a carboxylic acid which forms a fine suspension or a homogeneous solution in the hydrocarbon solvent wherein the ratio of the salt equivalents to the moles of zirconium compound is from above 0 to about 4.0.

This is a continuation of U.S. Ser. No. 07/331,019, filed Mar. 29, 1989now abandoned, which is in turn a continuation of U.S. Ser. No.07/011,034, filed Mar. 25, 1987now abandoned; which is in turn acontinuation of U.S. Ser. No. 856,499, filed now abandoned; which is inturn a divisional of U.S. Ser. No. 761,876, filed Aug. 2, 1985, nowabandoned.

BACKGROUND OF THE INVENTION

This invention relates to an improved process for preparing linearolefins, particularly linear alpha olefins. More particularly, thisinvention relates to an improved process for oligomerizing ethylene orpropylene or other alpha olefins to obtain oligomers which are linearolefins having from about 4 to about 20 carbon atoms. This inventionalso relates to a method for polymerizing or copolymerizing these linearolefins to produce higher molecular weight polymers.

U.S. Pat. No. 4,442,309, issued to Arthur W. Langer, Jr. on Apr. 10,1984, is one of several patents assigned to Exxon Research & EngineeringCompany which discloses a method for preparing linear olefins of thetype prepared according to the present invention. This referencediscloses the polymerization of ethylene in the presence of a catalystcomprising the reaction product of a zirconium transition metal halideand an aluminum alkyl compound The polymerization reaction takes placein the presence of a diluent such as chlorobenzene, dichlorobenzene,chlorotoluene, aromatics such as benzene, toluene, and xylene, andaliphatics such as pentane and heptane. The reaction temperature isabout 75° to 200° C. and the ethylene pressure is above 50 psia whilethe mole ratio of ethylene to olefin reaction products is maintainedabove about 0.8 throughout the reaction. The process disclosed in thepatent requires the step of killing catalyst activity after at leastabout 5 weight percent, based on diluent, of product olefin has formedby adding an agent or agents to kill the polymerization activity,thereby preventing or inhibiting deleterious side reactions. Typicalkilling agents mentioned are water, alcohol, carboxylic acids andphenols. The patent also states that a neutralizing agent must be usedto neutralize the Friedel-Crafts activity of the catalyst which remainsa problem even after polymerization activity is killed. Neutralizingbases which can be used include any Lewis base, i.e. alkali metal andalkyline earth metal hydroxides and carbonates, ammonium hydroxide, andammonia among others.

Russian Inventor's Certificate No. SU104-701-A discloses a catalyst forethylene oligomerization. The catalyst is comprised of zirconium saltsof carboxylic acids and an alkyl aluminum sesquichloride. It is saidthat oligomerization can take place at 5 to 30 atmospheres and 60° to100° C. in an aromatic solvent. When this reaction is carried out andthe reactor is opened after completion thereof, the reaction mixturebecomes yellow, fuming and the amount of olefin rapidly decreases withtime due to Friedel-Crafts alkylation of the solvent. In order toprevent loss of the olefin, the reaction mixture has to be cooled andneutralized as suggested in the Langer, Jr. patent discussed above.

It is an object of the present invention to provide a method forproducing linear olefins with a zirconium catalyst wherein the processcan be carried out to completion without the necessity of prematurelykilling the polymerization activity by the addition of a polymerizationkilling agent as characterized in the patent to Langer, Jr. It isanother object of this invention to provide a process for the productionof linear olefins which can be carried out to completion without theaddition of neutralizing agents to the reaction mixture to preventFriedel-Crafts type reactions which result in the loss of the olefinproduct. Still another object is to have an additive which will not killsubsequent polymerizations with other Ziegler catalysts.

SUMMARY OF THE INVENTION

This invention relates to a process for the preparation of linearolefins (oligomers) which comprises polymerizing (oligomerizing)ethylene, propylene or other alpha olefins in a hydrocarbon solvent at atemperature of 50°-150° C., preferably 50°-100° C., in the presence of acatalyst comprising a zirconium metal compound, an organometalliccompound wherein the metal is selected from the group consisting ofzinc, magnesium and aluminum, and a basic salt of a carboxylic acidwhich forms a fine suspension or a homogeneous solution in thehydrocarbon solvent and, as a reaction product with said zirconium metalcompound, forms a homogeneous solution or a fine suspension in thesolvent. Up to four equivalents of the salt can be used per mole of thezirconium compound.

The zirconium metal compounds may have the formula:

    ZrX.sub.n Y.sub.4-n

wherein X is a halogen, Y is selected from the group consisting ofaryloxides, alkoxides and carboxylates, and n ranges from 1 to 4. Mostpreferably, the zirconium compound is zirconium tetrachloride because itis less expensive and can be purchased in sufficient purity.

The hydrocarbon solvent may be selected from the group consisting ofaromatic, saturated, partially unsaturated, partially halogenated,partially oxygenated hydrocarbons and mixtures thereof. Most preferably,the solvent is toluene or a xylene.

The organometallic compound may be selected from the group consisting ofaluminum, zinc and magnesium alkyls, preferably alkyl aluminumsesquihalides, aluminum trialkyls or alkyl aluminum dihalides. Mostpreferably, the organometallic compound is ethyl aluminum sesquichlorideor ethyl aluminum dichloride.

The basic salt may be selected from the group consisting of lithium,sodium, potassium, magnesium, calcium, zinc or aluminum salts ofsaturated, unsaturated, or aromatic carboxylic acids. Preferably, thebasic salt is selected from the group consisting of lithium and calciumsalts of aromatic carboxylic acids such as benzoate and aliphaticcarboxylic acids such as stearate. Most preferably, the basic salt iscalcium stearate.

The present invention also relates to catalysts for the polymerizationof ethylene to form linear olefins. Also, this invention relates to theprocess for the production of such linear olefins and the furtherpolymerization thereof to form higher molecular weight polymers andcopolymers.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1. Graph of the Effect of Calcium Stearate on the OlefinOligomerization Reaction of Example I.

FIG. 2. Graph of the Effect of Ethyl Aluminum Sesquichloride on theOlefin Oligomerization Reaction of Example II.

FIG. 3. Graph of the Effect of Pressure on the Olefin Oligomerization ofExample III.

FIG. 4. Gas Chromatograph of the Polymerization Reactions of Example IV.

DETAILED DESCRIPTION OF THE INVENTION

The method of preparing the catalyst used in the process of the presentinvention is relatively simple. The zirconium metal compound is combinedwith the basic salt by placing both of them in a hydrocarbon solvent inwhich the zirconium metal compound and the basic salt for either a finesuspension or a homogenous solution. It is preferred that their reactionproduct form a fine suspension or a homogeneous solution in thehydrocarbon solvent.

The amount of the basic salt which is present in the catalyst is crucialto the performance thereof. Even small amounts of the basic salt willprevent some Friedel-Crafts alkylation but it is preferable that fromabout 1.6 to about 2.4 equivalents of the basic salt be used per mole ofzirconium compound. It appears that the best results are achieved whenabout 2 equivalents of the basic salt are used per mole of zirconiumcompound. For calcium salts, this corresponds to a mole ratio of about1:1 (Ca:Zr) and for lithium salts, it corresponds to a mole ratio ofabout 2:1 (Li:Zr). Generally, when the ratio of salt equivalents tomoles of zirconium is less than about 1.6:1 some Friedel-Craftsalkylation does take place and the yield of linear olefin suffers. Ifthis ratio is more than about 2.4:1, then the productivity of thecatalyst is not as efficient. If the ratio of salt equivalents to molesof zirconium is more than 4.0:1 then the advantages of the invention arelost because the productivity of the catalyst is drastically decreased.

The combined zirconium metal compound-basic salt catalyst component isactivated with an organometallic compound which contains either zinc,magnesium or aluminum. The method of addition of the organometalliccompound to the catalyst component is not particularly important and anyone of a variety of methods including neat or solution of organometallicsaturates in hydrocarbon or aromatic solvent can be used. It ispreferred that the organometallic compound used be one that allows afine suspension or a homogeneous solution in the hydrocarbon solventused to be maintained in the process. The mole ratio of organometalliccompound to zirconium metal compound should be in the range from about2:1 to about 20:1, preferably from about 6:1 to about 15:1, mostpreferably about 10:1 because the highest productivity is in thisregion.

As discussed above, a wide variety of hydrocarbon solvents are useful inthe present invention. Specific hydrocarbon solvents which can be usedare toluene, xylene, mesetylene, heptane and hexane. Toluene ispreferred because many of the salts form homogeneous solutions or finedispersions in the solvent. Also, the productivity is higher than withxylene. There are also a large number of zirconium metal compounds whichcan be used as the catalyst component in this invention. The preferredzirconium metal compound is zirconium tetrachloride because it isrelatively pure and inexpensive, but zirconium tetrabromide and mixedsalts of zirconium can also be used. The organometallic compound is alsoselected from a group of a rather wide scope depending upon the choiceof zirconium metal compound and basic salt. Ethyl aluminumsesquichloride and ethyl aluminum dichloride are preferred because theyprovide lower alpha olefins and triisobutyl aluminum and diethylaluminumchloride, among others may also be used. Also, the basic salt may beselected from a large group, depending upon the selection of the othercomponents. Calcium stearate is preferred because it partially dissolvesin the solvents of choice and other carboxylic acid salts such ascalcium, lithium, sodium, magnesium, and aluminum benzoates may be usedas well as the stearates thereof and other such acids having from 2 to20 carbon atoms. The solvent, zirconium compound, and the basic salt arechosen on the basis of their ability to form a homogeneous solution or afine suspension with each other.

It is theorized that one of the principal reasons why the process andcatalyst of the present invention achieves the desired results ofcontinuous polymerization and high catalyst activity without thenecessity for catalyst killing or neutralization is that all of thecomponents of the catalyst and preferably their various reactionproducts form a homogeneous overall catalyst composition in thehydrocarbon solvent of choice. This allows the desired reaction toproceed continuously without the disruption which might be caused by oneof the components falling out of solution or suspension. Furthermore,intimate mixture of the base with the zirconium compound can beeffective.

It is theorized that the presence of the basic salt in the catalystprevents the isomerization of alpha olefins to internal olefins whichwill not polymerize. Also, it is theorized that the basic saltneutralizes the acid components present in the catalyst which are theprimary cause of the Friedel-Craft reactions to undesirable sideproducts. In the case of a zirconium chloride catalyst, for example, thenegative ion of the basic salt most likely replaces the chloride duringthe reaction while the metal ion from the salt takes up the chloride.Addition of the corresponding carboxylic acid would produce free HCIwhich would cause isomerization and Friedel-Crafts alkylation.

The linear olefins (oligomers) produced according to the process of thepresent invention may then be used in a further polymerization processto produce higher molecular weight polymers and copolymers. The presentinvention contemplates a continuous process wherein ethylene, propyleneor other alpha olefins are polymerized as described above to producelinear olefins which are then exposed to a polymerization catalyst suchas a Ziegler-Natta catalyst containing titanium trichloride and diethylaluminum chloride or a supported catalyst with a titaniumchloride-magnesium chloride supported catalyst component combined withtrialkyl aluminum Other monomers such as ethylene, propylene,4-methyl-1-pentene, 1-butene, 1-hexene, 1-octene, etc. may be added tothe polymerization reactor and the polymerization is carried out undernormal polymerization conditions such as temperatures from about 50° C.to about 150° C. and pressures from about 5 atm. to about 500 atm. Thismethod is particularly applicable to the manufacture of linear lowdensity polyethylene products which are actually copolymers of ethyleneand alpha olefins having 4 or more carbon atoms. The catalysts andprocesses used to make linear low density poly- ethylene and otherpolymers and copolymers of linear olefins are well known.

EXAMPLE I

A series of polymerizations (oligomerizations) were carried out in astainless steel autoclave reactor at an ethylene pressure of 9atmospheres and a temperature of 75°-80° C. Toluene was used as thesolvent and it was deoxygenated and dried with molecular sieves. Calciumstearate was added to zirconium tetrachloride and toluene and stirredtogether. The catalyst was activated by adding ethyl aluminumsesquichloride to the reaction mixture and ethylene was pressured intothe reactor and maintained at 9 atmospheres. The mole ratio of ethylaluminum sesquichloride to zirconium tetrachloride was 10:1. Thedifferent catalyst components had different molar ratios of calciumstearate to zirconium tetrachloride. As can be seen by reviewing thegraph in FIG. 1, the productivity in terms of grams of ethylene consumedper gram of zirconium tetrachloride increases as the mole ratioincreases from 0 to about 1.0 and then it begins to fall off. Further,it is noted that at ratios lower than 0.8, the reaction mixture turnedyellow on exposure to air which is evidence of Friedel-Craftsalkylation. Therefore, the optimum range for the mole ratio of calciumstearate to zirconium tetrachloride is from about 0.8 to about 1.2 (saltequivalents/ moles zirconium ratio is 1.6-2.4).

EXAMPLE II

The procedure of Example I was repeated in several polymerizations whilethe mole ratio of ethyl aluminum sesquichloride to zirconiumtetrachloride was varied. The mole ratio of calcium stearate tozirconium tetrachloride was 1:1.

As can be seen by reviewing FIG. 2, the productivity of the catalystincreases as the molar ratio of ethyl aluminum sesquichloride tozirconium tetrachloride increases from 6 to 10 but falls off as theratio is increased from 10 to 15. The optimum molar ratio appears to bearound 10.

EXAMPLE III

The procedure of Example I was repeated for two oligomerizations whereinthe ratio of calcium stearate to zirconium tetrachloride was 1:1 and theratio of ethyl aluminum sesquichloride to zirconium tetrachloride was10:1. In the first oligomerization, an ethylene pressure of 9atmospheres was used and in the second oligomerization an ethylenepressure of 17 atmospheres was used. The productivity of the catalystranged from 67.4 grams of oligomer per gram of zirconiumhours-atmopshereto 71.2 grams. By referring to the graph in FIG. 3, it can be seen thatthe affect of pressure on the oligomerization reaction is generallylinear.

EXAMPLE IV

Four polymerizations were carried out essentially in accordance with theprocedure of Example I. In Experiment A, the procedure was the sameexcept that no calcium stearate was used. In Experiment B, the moleratio of calcium stearate to zirconium chloride was 0.2. In ExperimentC, heptane was used as the solvent instead of toluene and the mole ratioof calcium stearate to zirconium tetrachloride was 1:1. In Experiment D,the exact procedure of Example I was used and the mole ratio of calciumstearate to zirconium tetrachloride was 1.1.

The reaction products from these four experiments were characterized bygas chromatographic (GC) analysis. The results are shown in FIG. 4. Theanalysis of the reaction product of Experiment A indicated the presenceof unique peaks not accountable by comparison to alpha olefins. Thepeaks (3.98, 5.51, and 6.22) are indicative of Friedel-Crafts reactionproducts of the olefin with the toluene solvent. These were identifiedby gas chromotography mass spectrum (GCMS) analysis. GCMS analysis wasused to prove alkylation occurred with toluene and without salt. Theanalysis of the reaction product of Experiment B shows similar peaks(3.78 and 5.38) but they are considerably smaller. It also shows at peakat 2.68 which is indicative of some alpha olefin production. Theanalysis for the reaction product of Experiment C indicates noFriedel-Crafts products peaks but the peaks indicative of alpha olefins(0.34 hexene, 0.95 toluene, 1.20 octene, 2.72 decene, 4.44 dodecene,6.30 tetradecene, 7.88 hexadecene, 9.32 octadecene) are very small sothe yield of such olefins is relatively low.

The analysis of the reaction product of Experiment D indicates thatthere are no unusual Friedel-Crafts peaks and also shows that the peakscharacteristic of alpha olefins (0.33, 1.24, 2.74, 4.55, 6.24, 7.77 and9.16) are relatively large, indicating a high yield of such olefins.Therefore, it can be seen that the preferred process of the presentinvention, as exemplified by Experiments C and D, does produce alphaolefins without the accompanying undesirable FriedelCrafts reactionproducts which, in prior art processes such as that disclosed in U.S.Pat. No. 4,442,309, can only be prevented by the addition ofpolymerization killing agents and neutralizing agents subsequent topolymerization or addition of components which might kill furtherpolymerization with other catalysts.

EXAMPLE V

In this experiment, the procedure described in Russian Inventor'sCertificate No. SU1042-701-A was duplicated. To a solution of 50 mil oftoluene and 2.0 m mole (0.242 g) benzoic acid was added 0.5 m mole(0.1165 g) ZrCl₄. The mixture was stirred for 1 hour and 6 m moles ofethyl aluminum sesquichloride (in heptane 25%) was added. The mixturewas transferred to a 1 liter autoclave reactor and charged with ethyleneat 9 atmospheres and heated to 75°-83° C. Ethylene pressure wasmaintained throughout. Approximately 26 grams of ethylene was consumed.

When the reactor was opened, the reaction mixture became yellow andfuming, and the amount of olefin present rapidly decreased with time dueto, it is theorized, Friedel-Crafts alkylation of the solvent. This wasconfirmed by GCMS of the reaction mixture. In order to be able tocharacterize the olefins, the reaction mixture had to be cooled andneutralized with aqueous potassium carbonate, as suggested in the Exxonpatent, to prevent yellowing and alkylation. Without neutralization,ring alkylation was observed by GCMS analysis. Thus, it can be seen thatthis prior art process cannot accomplish the objectives of the presentinvention without neutralization with potassium carbonate or otheralkaline compounds.

EXAMPLE VI

A series of oligomerizations were carried out using 25 ml of mixedxylenes, 0.42 m moles (0.10 g) ZrCl₄, salt as described in Table 1 and3.75 m moles of ethyl aluminum sesquichloride. Reactions were run for 1hour at 75° C. and 11.2 atmospheres of ethylene pressure. From the tableit can be seen that calcium and lithium salts afford cleaner productsand that calcium stearate is a preferred adduct. Compared to the methodof the Exxon patent, which uses carboxylic acids as adducts, the cationseems to control the degree of isomerization as well increasing theproductivity of the catalyst.

                                      TABLE 1                                     __________________________________________________________________________    EFFECT OF SALT ON OLIGOMERIZATION                                                                         GAS                                               SALT.sup.c                                                                         GRAMS                                                                              M MOLES                                                                              YIELD (g)                                                                           G/G Zr                                                                             CHROMATOGRAPHY                                    __________________________________________________________________________    Ca(Bz).sub.2                                                                       0.14 0.41   17.2 g                                                                              441  Normal                                            Ca(St).sub.2                                                                       0.25 0.41   16.8  431  Normal                                            NaBz 0.14 0.98   1.6    41  Isomerization.sup.a                               NaSt 0.24 0.78   6.7   172  Isomerization.sup.a                               LiBz 0.11 0.86   11.2  287  Normal                                            LiSt 0.24 0.83   9.0   231  Normal                                            Mg(Bz).sub.2                                                                       0.13 0.41   6.7   172  Isomerization.sup.a                               Mg(St).sub.2                                                                       0.24 0.41   8.4   215  Isomerization.sup.a                               Al(St).sub.3                                                                       0.24 0.28   13.6  349  Isomerization.sup.a                               --   --   --     --    --   --                                                Ca(St).sub.2                                                                       0.25 0.41.sup.b                                                                           34.5  885  Normal                                            Mg(St).sub.2                                                                       0.24 0.41.sup.b                                                                           16.5  423  Slight                                                                        Isomerization                                     Mg(St).sub.2                                                                       0.24 0.41.sup.b                                                                           17.0  436  Slight                                                                        Isomerization                                     LiBz 0.11 0.86.sup.b                                                                           --    --   Normal                                            __________________________________________________________________________     .sup.a Yellow color FriedelCrafts Alkylation.                                 .sup.b Toluene rather than xylenes as solvent.                                .sup.c Bz = benzoate St = stearate                                       

EXAMPLE VII

In the next five examples, ethylene-oligomer copolymers were prepared bysynthesizing the olefins using optimum conditions according to theprocedure of Example I and then injecting catalyst and an aluminum alkylinto the reaction mixture. In the first experiment, 11.7 g of olein wasprepared. The reactor was cooled to -5° C. and ethylene was vented. Then0.1 g of a titanium on silica catalyst, 3 m moles of triethyl aluminumand 20 ml of heptane were injected into the reactor. Ethylene at 11.2atmospheres was charged into the reactor and the polymerization wasallowed to proceed at 80°-85° C. for 1 hour. At that time 46.8 g ofethylene was consumed. The reactor was vented and the polymer was driedand isolated to yield 57.8 g of material. The polymer had a density of0.9191 and 8% branching by infrared analysis.

EXAMPLE VIII

Two runs were carried out in a similar manner to Example VII using adifferent titanium silica catalyst and afforded polymers with0.9292-0.9318 density and 3.3-6.5 short chain branches/1000 carbonatoms.

EXAMPLE IX

A run was carried out using a titanium chloride and magnesium chloridesupported catalyst and triethyl aluminum as the catalyst activator. Inthe oligomerization, 6.6 grams of olefin were consumed and in thepolymerization 34.2 grams of ethylene were consumed. The actual polymerweighed 39.5 grams and had 7.9 short chain branches/1000 carbon atoms.

EXAMPLE X

In this experiment, 19.8 g of olefin was prepared. Then, without coolingthe reactor or stopping the reaction, 50 mg of a catalyst (prepared byextensive ball-milling of TiCl₃ AA with butyl benzoate) and 4.5 m molesof triethyl aluminum in 6 ml of heptane was added. Polymerization wasallowed to proceed for 1 hour until another 27.8 g of ethylene wasconsumed. The reactor was vented and the polymer isolated and dried toyield 49.3 g of material with a density of 0.8886 and 17.8% branching.

EXAMPLE XI

In this experiment, 50 mg of the catalyst described in Example X wasadded to the reactor before oligomerization took place. Then 24.9 g ofethylene was oligomerized. The reactor was cooled to -5° C. and theethylene was vented off. A small amount of the mixture was analyzed bygas chromatography and this showed that a normal oligomerization hadoccurred. Then 6 m moles of triethyl aluminum and 7 ml of heptane wereadded. The reactor was pressured with ethylene and heated to 90° C. andpolymerization occurred until another 64.3 g of ethylene was consumed.The polymer was isolated and weighed 95.6 g. It had a density of 0.9075and 11.6% branching. These experiments (Examples VII-IX) indicate theolefins produced by my process are of polymerization grade qualitywithout the necessity of purification and that they do not poisonethylene polymerization catalysts.

EXAMPLE XII

A propylene-oligomer copolymer was prepared as follows. By conditionsdescribed previously (in Example I) 20.7 g of ethylene was oligomerized.The reactor was cooled to -10° C. and vented. To the reactor was added100 mg of the catalyst described in Example X as well as 3.75 m moles oftriethyl aluminum in 12.5 ml of heptane. The reactor pressured to 9.5atmospheres of propylene and heated to 70° C. Polymerization took placeuntil 36.6 g of propylene was consumed. The reactor was vented and thepolymer isolated and dried to give 58.9 g of copolymer which had 68%propylene by carbon 13 nuclear magnetic resonance spectroscopy. Thespectrum was consistent with a random, rather than a block, copolymer.

I claim:
 1. A catalyst active for oligomerizing one or moreoligomerizable alpha olefin monomers in a hydrocarbon solvent to producelinear olefin oligomers of from about 4 to about 20 carbon atoms, saidoligomerization catalyst comprisingan organometallic compound whereinthe metal thereof is selected from the group consisting of zinc,magnesium, and aluminum, in combination with the reaction mixtureobtained by reacting in a hydrocarbon, (a) a zirconium compound of theformula ZrX_(n) Y_(4-n) wherein X is a halogen, Y is selected from thegroup consisting of aryloxides, alkoxides, and carboxylates, and nranges from 1 to 4, inclusive, and (b) a basic salt of a carboxylicacid, wherein the ratio of basic salt equivalents to moles of zirconiumcompound in said oligomerization catalyst is from above zero to about4.0:1 and the amount of said basic salt is sufficient to inhibitFridel-Crafts alkylation during said oligomerization, said basic saltforming a fine suspension or homogenous solution with said solvent. 2.The catalyst of claim 1 wherein the zirconium compound is Z₄ Cl₄.
 3. Thecatalyst of claim 1 wherein the organometallic compound is selected fromthe group consisting of aluminum, zinc and magnesium alkyls.
 4. Thecatalyst of claim 3 wherein the organometallic compound is an alkylaluminum sesquihalide, an aluminum trialkyl, of an alkyl aluminumdihalide.
 5. The catalyst of claim 4 wherein the organometallic compoundis ethyl aluminum sesquichloride or ethyl aluminum dichloride.
 6. Thecatalyst of claim 1 wherein the mole ratio of organometallic compound tozirconium compound is from about 2:1 to about 20:1.
 7. The catalyst ofclaim 6 wherein the mole ratio of organometallic compound to zirconiumcompound is from about 6:1 to about 15:1.
 8. The catalyst of claim 1wherein the basic salt is selected from the group consisting of lithium,sodium, potassium, magnesium, calcium, zinc or aluminum salts ofsaturated, unsaturated or aromatic carboxylic acids.
 9. The catalyst ofclaim 8 wherein the basic salt is selected from the group consisting oflithium and calcium salts of carboxylic acids having from 2 to 20 carbonatoms.
 10. The catalyst of claim 9 wherein the basic salt is calcium orlithium stearate.
 11. The catalyst of claim 1 wherein the zirconiumcompound is ZrCl₄, the organometallic compound is ethyl aluminumsesquichloride or ethyl aluminum dichloride, and the basic salt iscalcium stearate.
 12. The catalyst of claim 1 wherein the ratio of saltequivalents to moles of zirconium compound is from about 1.6:1 to about2.4:1.